Sealant compositions and methods utilizing nano-particles

ABSTRACT

The present invention includes well treatment fluids and methods utilizing nano-particles and, in certain embodiments, to sealant compositions and methods utilizing nano-particles. The nano-particles may be incorporated into the sealant composition in different forms, including as discrete nano-particles, encapsulated nano-particles, agglomerated nano-particles, or in a liquid suspension.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 12/567,783, filed Sep. 27, 2009, entitled “Sealant Compositions andMethods Utilizing Nano-Particles,” which is a continuation-in-part ofU.S. patent application Ser. No. 12/263,954, filed Nov. 3, 2008,entitled “Cement Compositions and Methods Utilizing Nano-HydraulicCement,” which is a continuation-in-part of U.S. patent application Ser.No. 11/747,002, now U.S. Pat. No. 7,559,369, filed on May 10, 2007,entitled “Well Treatment Compositions and Methods UtilizingNano-Particles.” The entire disclosures of these applications areincorporated herein by reference.

BACKGROUND

The present invention relates to well treatment fluids and methodsutilizing nano-particles and, in certain embodiments, to sealantcompositions and methods utilizing nano-particles.

A variety of different sealant compositions may be used in subterraneanoperations. For example, in subterranean well construction, a pipestring (e.g., casing and liners) may be run into a well bore andcemented in place using a cement composition. The process of cementingthe pipe string in place is commonly referred to as “primary cementing.”In a typical primary cementing method, a cement composition may bepumped into an annulus between the walls of the well bore and theexterior surface of the pipe string disposed therein. The cementcomposition sets in the annular space, thereby forming an annular sheathof hardened, substantially impermeable cement that supports andpositions the pipe string in the well bore and bonds the exteriorsurface of the pipe string to the subterranean formation. Among otherthings, the annular sheath of set cement surrounding the pipe stringshould seal the annulus, preventing the migration of fluids in theannulus, as well as protecting the pipe string from corrosion. Cementcompositions also may be used in remedial cementing methods, such assqueeze cementing, repairing casing strings and the placement of cementplugs. In squeeze cementing, for example, a cement composition may beused to plug off and seal undesirable flow passages in a cement sheath,casing, and/or gravel packs. In some instances, cement compositions maybe used to change the direction of the well bore, for example, bydrilling a pilot hole in a hardened mass of cement, commonly referred toas a “kickoff plug,” placed in the well bore. While a cement compositionis one type of sealant composition that may be used in subterraneanoperations, other non-cement containing cement sealant compositions alsomay be employed. By way of example, polymeric sealant compositions alsomay be used.

SUMMARY

The present invention relates to well treatment fluids and methodsutilizing nano-particles and, in certain embodiments, to sealantcompositions and methods utilizing nano-particles.

An embodiment of the present invention includes a method comprisingintroducing a sealant composition comprising nano-particles and waterinto a subterranean formation. The nano-particles may comprise at leastabout 75% by weight of dry particles in the sealant composition.

Another embodiment of the present invention includes a method comprisingpreparing a sealant composition comprising nano-particles and water. Thenano-particles may comprise at least about 20% by weight of dryparticles in the sealant composition. At least a portion of thenano-particles may be introduced into the sealant composition in aliquid suspension.

Another embodiment of the present invention includes a method comprisingincluding agglomerated nano-particles in a sealant composition. Themethod further may comprise introducing the sealant composition into asubterranean formation.

Another embodiment of the present invention includes a method comprisingintroducing a sealant composition comprising nano-particles, water, andan elastomeric particle into a subterranean formation.

Another embodiment of the present invention includes a method comprisingintroducing a sealant composition comprising nano-particles, water, anda swellable particle into a subterranean formation.

Yet another embodiment of the present invention includes a sealantcomposition comprising nano-particles and water. The nano-particles maycomprise at least 75% by weight of dry particles in the sealantcomposition.

The features and advantages of the present invention will be apparent tothose skilled in the art upon reading the following description ofspecific embodiments.

DESCRIPTION OF SPECIFIC EMBODIMENTS

The present invention relates to well treatment fluids and methodsutilizing nano-particles and, in certain embodiments, to sealantcompositions and methods utilizing nano-particles. As used herein, theterm “sealant composition(s)” refers to a composition(s) thathydraulically sets or otherwise develops compressive strength suitablefor use in a subterranean formation application.

An embodiment of the sealant compositions of the present invention maycomprise nano-particles and water. Generally, the term “nano-particle”may be defined as a particle having a mean particle size of about 1nanometers (“nm”) to about 100 nm (e.g., about 5 nm, about 10, about 20nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm,about 80 nm, about 90 nm, etc.). In accordance with embodiments of thepresent invention, the nano-particles may be included in the sealantcompositions in a number of different forms, including, for example, asdiscrete nano-particles, encapsulated nano-particles, agglomeratednano-particles, or in a liquid suspension. In certain embodiments, thenano-particles may comprise at least about 1% by weight of the dryparticles in the sealant composition. The term “dry particles” refers tothe nano-particles and other solid particles that are present in a dryform at some point either prior to or during introduction into thesealant composition. In certain instances, the dry particles may besuspended in a liquid medium prior to introduction in the sealantcomposition.

One of the many potential advantages of using nano-particles inembodiments of the sealant compositions is that the inclusion ofnano-particles can provide sealant compositions having improvedmechanical properties after setting. For example, embodiments of thesealant compositions may have improved compressive strength, tensilestrength, Young's modulus and Poisson's ratio. In addition,nano-particles (e.g., nano-silica) also may be included in sealantcompositions as a set accelerator to accelerate the set time of thesealant composition. Among other advantages of using nano-particles isthat since nano-particles are small, the nano-particles should becapable of invading narrow opening that standard cements may not be ableto access. Accordingly, sealant compositions comprising nano-particlesmay be suitable for use, for example, in squeeze operations. Forexample, embodiments of the sealant compositions may be seal voids in apipe string, cement sheath, or gravel pack. As used herein, the term“void” refers to any type of space, including fractures, holes, cracks,spaces, channels, and the like. It is believed that the nano-particlesshould be able to penetrate voids that are not repairable withlarger-sized cements.

Examples of suitable nano-particles may include nano-hydraulic cements,nano-silicas, nano-clays, nano-alumina, nano-zinc oxide, nano-boron,nano-iron oxide and combinations thereof. Nano-hydraulic cements have avariety of applications for well cementing, including both primary andremedial cementing operations. A suitable nano-hydraulic cement andtechnique that may be used to measure particle size, in accordance withembodiments of the present invention, is described by S C Halim, T JBrunner, R N Grass, M Bohner and W J Stark, Preparation of an Ultra FastBinding Cement from Calcium Silicate-Based Mixed Oxide Nanoparticles,NANOTECHNOLOGY 18 (2007) 395701 (6pp). Among other advantages of usingnano-hydraulic cement is that it should provide a sealant compositionwith a lower density and reduced set time. It is believed that thereduced set time of the nano-hydraulic cement may be from earlyreactivity.

Generally, any hydraulic cement suitable for use in subterraneanoperations and sized to a range of about 1 nm to about 100 nm may besuitable for use as a nano-hydraulic cement in embodiments in thepresent invention. Suitable cements that may, for example, be ground tonano-hydraulic cements include those classified as Classes A through Haccording to American Petroleum Institute, API Specification forMaterials and Testing for Well Cements, API Specification 10, Fifth Ed.,Jul. 1, 1990. In certain embodiments, API Class A, C, G and H hydrauliccements may be preferred. In addition, in some embodiments, othercements that may be suitable for grinding to nano-hydraulic cementssuitable for use in the present invention may be classified as ASTM TypeI, II, or III. A variety of nano-hydraulic cements are suitable for use,including those comprised of calcium, aluminum, silicon, oxygen, and/orsulfur, which set and harden by reaction with water. Such nano-hydrauliccements include, but are not limited to, Portland cements, pozzolaniccements, gypsum cements, soil cements, calcium phosphate cements,high-alumina content cements, silica cements, high-alkalinity cements,or mixtures thereof.

The nano-hydraulic cement may be present in embodiments of the sealantcompositions of the present invention in an amount of from about 0.01%to 100% by weight of cementitious material. As used herein, the term“cementitious material” refers to nano-hydraulic cement, hydrauliccement, cement kiln dust, and the like, which set and harden by reactionwith water. In some embodiments, the nano-hydraulic cement may bepresent in the sealant compositions of the present invention in anamount of about 1% to 75% by weight of cementitious material (e.g.,about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about60%, about 70%, etc.). In some embodiments, the nano-hydraulic cementmay be present in the sealant compositions of the present invention inan amount of about 1% to about 50% by weight of cementitious material.In some embodiments, the nano-hydraulic cement may be present in thesealant compositions of the present invention in an amount of about 1%to about 25% by weight of cementitious material.

Another example of a suitable nano-particle that may be included inembodiments of the sealant compositions of the present inventionincludes nano-silica. It is now recognized that the nano-silica utilizedwith present embodiments, which may include silicon dioxide, may have animpact on certain physical characteristics of sealant compositions aftersetting. For example, relative to inclusion of colloidal silica orlarger silica particles in a sealant composition, inclusion ofparticulate nano-silica in the sealant composition may provide improvedmechanical properties, such as compressive strength, tensile strength,Young's modulus and Poisson's ratio. In addition, particulatenano-silica also may be included in the sealant composition as a setaccelerator to accelerate the set time of the sealant composition.Accordingly, a sealant composition in accordance with presentembodiments may comprise a sufficient amount of nano-silica to providethe desired characteristics. In certain embodiments, the nano-silica maybe present in the sealant compositions in an amount in the range of fromabout 1% to about 25% by weight of cementitious materials (e.g., about2%, about 5%, about 10%, about 15%, about 20%, etc.). In certainembodiments, the nano-silica may be present in the sealant compositionsin an amount in the range of from about 5% to about 15% by weight ofcementitious materials.

The nano-silica may, for example, be described as particulatenano-silica. That is, the nano-silica may be particulate in nature andnot, for example, a colloidal silica or a suspension of silica insolution. Indeed, in one embodiment, the particulate nano-silica may beadded to the sealant composition as a dry nano-silica powder. However,colloidal nano-silica also may be suitable for use in embodiments of thepresent invention. In certain embodiments, the nano-silica may have amean particle size of less than about 100 nm, for example, in the rangeof from about 1 nm to about 100 nm. In further embodiments, thenano-silica may have a mean particle size of less than about 50 nm, forexample in the range of from about 5 nm to about 50 nm. In furtherembodiments, the nano-silica may have a particle size of less than orequal to about 30 nm, for example, in the range of from about 5 nm toabout 30 nm. However, it should be noted that the nano-silica may beutilized in combination with larger sized silica particles in accordancewith present embodiments.

Another example of a suitable nano-particle that may be included inembodiments of the sealant compositions of the present inventionincludes nano-clay. An example of a suitable nano-clay includesnano-bentonite. In one particular embodiment, the nano-clay may comprisenano-montmorillonite. Nano-montmorillonite is member of thesmectite-clay family, and belongs to the general mineral group of clayswith a sheet-like structure where the dimensions in two directions farexceed its thickness. Generally, the nano-montmorillonite has of athree-layered structure of aluminum sandwiched between two layers ofsilicon, similar to the mica-type layered silicates. Montmorillonite isan active and major ingredient in a volcanic ash called bentonite, whichhas an ability to swell to many times its original weight and volumewhen it absorbs water. One example of a suitable nano-montmorillonite isNANOMER® nanoclay, which is available from Nanocor, Arlington Heights,Ill.

It is now recognized that the nano-clay utilized with presentembodiments may have an impact on certain physical characteristics ofsealant compositions after setting. For example, relative to inclusionof larger clay particles in a sealant composition, inclusion ofnano-clay in particular sealant compositions may provide improvedmechanical properties. In addition, the nano-clay also may be includedin embodiments of the sealant composition to reduce the permeability ofthe resultant set cement, thus potentially reducing the susceptibilityof the set cement to problems associated with gas migration or corrosiveenvironments such as those created by CO₂. For example, a sealantcomposition may be designed to have reduced permeability after settingby including nano-clay in the sealant composition. Accordingly, asealant composition in accordance with present embodiments may comprisea sufficient amount of nano-clay to provide the desired characteristics.By way of example, the nano-clay may be present in the sealantcompositions in an amount in the range of from about 0.1% to about 25%by weight of cementitious components (e.g., about 0.5%, about 1%, about5%, about 10%, about 15%, about 20%, etc.). In certain embodiments, thenano-clay may be present in the sealant compositions in an amount in therange of from about 2% to about 10% by weight of cementitiouscomponents.

The nano-clay may be configured in any of a variety of different shapesin accordance with embodiments of the present invention. Examples ofsuitable shapes include nano-clay in the general shape of platelets,shavings, flakes, rods, strips, spheroids, toroids, pellets, tablets, orany other suitable shape. In certain embodiments, the nano-clay maygenerally have a plate-type structure. Suitable plate-type nano-claysinclude nano-montmorillonite. Plate-type nano-clay may have a thickness,in certain embodiments of less than about 10 nm and, alternatively, ofless than about 2 nm. In certain embodiments, the plate-type nano-claymay have a thickness of about 1 nm. Embodiments of the plate-typenano-clay may have surface dimensions (length and/or width) of about 1nm to about 600 nm. In certain embodiments, the plate-type nano-clay mayhave surface dimensions about 300 nm to about 600 nm. It should beunderstood that plate-type nano-clay having dimensions outside thespecific ranges listed in this disclosure are encompassed by the presentinvention.

As previously mentioned, the nano-particles may comprise at least about1% by weight of the dry particles (e.g., about 10%, about 25%, about50%, about 75%, about 80%, about 90%, about 99% etc.), that wereincluded in the sealant composition. By way of example, thenano-particles may be comprise about 10% to about 100% by weight of thedry particles that were included in the sealant composition. By way offurther example, the nano-particles may comprise about 50% about 100% byweight of the dry particles that were included in the sealantcomposition. It should be understood that the reference to dry particlesgenerally refers to a variety of different additives that may typicallybe included in a sealant composition in a solid form. Examples of suchadditives include, but are not limited to, hydraulic cement, cement kilndust, amorphous silica, crystalline silica, vitrified shale, lostcirculation materials, and the like. It should be not be implied fromthe term “dry particle” that the nano-particles or other dry particles(or solid particles) are dry when introduced into the sealantcomposition. In certain embodiments, the dry particles may be suspendedin a liquid medium prior to introduction in the sealant composition.

The water used in certain embodiments of the sealant compositions of thepresent invention may be freshwater or saltwater (e.g., water containingone or more salts dissolved therein, seawater, brines, saturatedsaltwater, etc.). In general, the water may be present in an amountsufficient to form a pumpable slurry. In certain embodiments, the watermay be present in the sealant compositions in an amount in the range ofabout 33% to about 200% by weight of cementitious materials. In certainembodiments, the water may be present in an amount in the range of about35% to about 70% by weight of cementitious materials.

Embodiments of the sealant compositions of the present invention mayfurther comprise a hydraulic cement that has a mean particle size ofgreater than about 1 micron. Generally, any of a variety of cementssuitable for use in subterranean cementing operations may be used inaccordance with embodiments of the present invention. Suitable examplesinclude hydraulic cements that comprise calcium, aluminum, silicon,oxygen and/or sulfur, which set and harden by reaction with water. Suchhydraulic cements, include, but are not limited to, Portland cements,pozzolana cements, gypsum cements, high-alumina-content cements, slagcements, and combinations thereof. In certain embodiments, the hydrauliccement may comprise a Portland cement. Portland cements that may besuited for use in embodiments of the present invention may be classifiedas Class A, C, H and G cements according to American PetroleumInstitute, API Specification for Materials and Testing for Well Cements,API Specification 10, Fifth Ed., Jul. 1, 1990. In addition, in someembodiments, hydraulic cements suitable for use in the present inventionmay be classified as ASTM Type I, II, or III.

Where present, the larger hydraulic cement generally may be included inembodiments of the sealant compositions in an amount sufficient toprovide the desired compressive strength, density, and/or cost. In someembodiments, the larger hydraulic cement may be present in the sealantcompositions of the present invention in an amount of about 0.1% toabout 99% by weight of cementitious materials. In some embodiments, thehydraulic cement may be present in the sealant compositions of thepresent invention in an amount of about 0.1% to about 75% by weight ofcementitious materials. In some embodiments, the hydraulic cement may bepresent in the sealant compositions of the present invention in anamount of about 0.1% to about 50% by weight by weight of cementitiousmaterials. In some embodiments, the hydraulic cement may be present inthe sealant compositions of the present invention in an amount in therange of from about 0.1% to about 25% by weight of cementitiousmaterials.

In certain embodiments of the present invention, a sealant compositiondescribed herein may be foamed using a gas and a foaming and stabilizingsurfactant. The gas utilized in the foamed sealant compositions of thepresent invention may be any gas suitable for foaming a sealantcomposition, including, but not limited to, air or nitrogen, orcombinations thereof. Generally, the gas should be present in the foamedsealant compositions of the present invention in an amount sufficient toform a suitable foam. In certain embodiments, the gas may be present inan amount in the range of from about 10% and about 80% by volume of thecomposition.

Any suitable foaming and stabilizing surfactant may be used in thefoamed sealant composition of the present invention. Among other things,the foaming and stabilizing surfactants may facilitate the foaming of asealant composition and/or also stabilize the resultant foamed sealantcomposition formed therewith. Suitable foaming and stabilizingsurfactants may include, but are not limited to: mixtures of an ammoniumsalt of an alkyl ether sulfate, a cocoamidopropyl betaine surfactant, acocoamidopropyl dimethylamine oxide surfactant, sodium chloride, andwater; mixtures of an ammonium salt of an alkyl ether sulfatesurfactant, a cocoamidopropyl hydroxysultaine surfactant, acocoamidopropyl dimethylamine oxide surfactant, sodium chloride, andwater; hydrolyzed keratin; mixtures of an ethoxylated alcohol ethersulfate surfactant, an alkyl or alkene amidopropyl betaine surfactant,and an alkyl or alkene dimethylamine oxide surfactant; aqueous solutionsof an alpha-olefinic sulfonate surfactant and a betaine surfactant; andcombinations thereof. An example of a suitable hydrolyzed keratin isdescribed in U.S. Pat. No. 6,547,871, the disclosure of which isincorporated herein by reference. Example of suitable mixtures of anethoxylated alcohol ether sulfate surfactant, an alkyl or alkeneamidopropyl betaine surfactant, and an alkyl or alkene dimethylamineoxide surfactant is described in U.S. Pat. No. 6,063,738, the disclosureof which is incorporated herein by reference. Examples of suitableaqueous solutions of an alpha-olefinic sulfonate surfactant and abetaine surfactant are described in U.S. Pat. No. 5,897,699, thedisclosure of which is incorporated herein by reference. In oneembodiment, the foaming and stabilizing surfactant comprises a mixtureof an ammonium salt of an alkyl ether sulfate, a cocoamidopropyl betainesurfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodiumchloride, and water.

Where used, the foaming and stabilizing surfactants may be present inembodiments of the foamed sealant compositions of the present inventionin an amount sufficient to provide a suitable foam. In some embodiments,the foaming and stabilizing surfactant may be present in an amount inthe range of from about 0.8% and about 5% by volume of the water presentin the foamed sealant composition.

Embodiments of the sealant compositions of the present invention mayalso comprise swellable particles. As used herein, a particle ischaracterized as swelling when it swells upon contact with oil and/or anaqueous fluid (e.g., water). Swellable particles suitable for use inembodiments of the present invention may generally swell by up to about50% of their original size at the surface. Under downhole conditions,this swelling may be more, or less, depending on the conditionspresented. For example, the swelling may be at least 10% at downholeconditions. In some embodiments, the swelling may be up to about 50%under downhole conditions. However, as those of ordinary skill in theart, with the benefit of this disclosure, will appreciate, the actualswelling when the swellable particles are included in a sealantcomposition may depend on, for example, the concentration of theswellable particles included in the sealant composition. In accordancewith embodiments of the present invention, the swellable particles maybe included in the sealant composition, for example, to counteract theformation of cracks in the cement sheath and/or micro-annulus betweenthe cement sheath and the pipe string or the formation. In general, theswellable particles should be capable of swelling when contacted byaqueous fluids and/or oil to inhibit fluid flow through the crack and/ormicro-annulus. Accordingly, the swellable particles may prevent and/orreduce the loss of zonal isolation in spite of the formation of cracksand/or micro-annulus, potentially resulting in an improved annular sealfor the sealant compositions.

An example of swellable particles that may be utilized in embodiments ofthe present invention comprises a swellable elastomer. Some specificexamples of suitable swellable elastomers include, but are not limitedto, natural rubber, acrylate butadiene rubber, polyacrylate rubber,isoprene rubber, choloroprene rubber, butyl rubber (IIR), brominatedbutyl rubber (BIIR), chlorinated butyl rubber (CIIR), chlorinatedpolyethylene (CM/CPE), neoprene rubber (CR), styrene butadiene copolymerrubber (SBR), sulphonated polyethylene (CSM), ethylene acrylate rubber(EAM/AEM), epichlorohydrin ethylene oxide copolymer (CO, ECO),ethylene-propylene rubber (EPM and EDPM), ethylene-propylene-dieneterpolymer rubber (EPT), ethylene vinyl acetate copolymer,fluorosilicone rubbers (FVMQ), silicone rubbers (VMQ), poly2,2,1-bicyclo heptene (polynorborneane), and alkylstyrene. One exampleof a suitable swellable elastomer comprises a block copolymer of astyrene butadiene rubber. Examples of suitable elastomers that swellwhen in contact with oil include, but are not limited to, nitrile rubber(NBR), hydrogenated nitrile rubber (HNBR, HNS), fluoro rubbers (FKM),perfluoro rubbers (FFKM), tetrafluorethylene/propylene (TFE/P),isobutylene maleic anhydride. Combinations of suitable swellableelastomers also may be used. Other swellable elastomers that behave in asimilar fashion with respect to oil or aqueous fluids also may besuitable. Those of ordinary skill in the art, with the benefit of thisdisclosure, will be able to select an appropriate swellable elastomerfor use in embodiments of the sealant compositions of the presentinvention based on a variety of factors, including the application inwhich the composition will be used and the desired swellingcharacteristics.

An example of swellable particles that may be utilized in embodiments ofthe present invention comprises a water-swellable polymer. Some specificexamples of suitable water-swellable polymers, include, but are notlimited to starch-polyacrylate acid graft copolymer and salts thereof,polyethylene oxide polymer, carboxymethyl cellulose type polymers,polyacrylamide, poly(acrylic acid) and salts thereof, poly(acrylicacid-co-acrylamide) and salts thereof, graft-poly(ethylene oxide) ofpoly(acrylic acid) and salts thereof, poly(2-hydroxyethyl methacrylate),and poly(2-hydroxypropyl methacrylate). Combinations of suitablewater-swellable polymers also may be used. In certain embodiments, thewater-swellable polymers may be crosslinked and/or lightly crosslinked.Other water-swellable polymers that behave in a similar fashion withrespect to aqueous fluids also may be suitable. Those of ordinary skillin the art, with the benefit of this disclosure, will be able to selectappropriate water-swellable polymers for use in embodiments of thesealant compositions of the present invention based on a variety offactors, including the application in which the composition will be usedand the desired swelling characteristics.

Where used, the swellable particles generally may be included in thesealant compositions in an amount sufficient to provide the desiredmechanical properties. In some embodiments, the swellable particles maybe present in the sealant compositions in an amount up to about 25% byweight of the cementitious component. In some embodiments, the swellableparticles may be present in the sealant compositions in a range of about5% to about 25% by weight of the cementitious component. In someembodiments, the swellable particles may be present in the sealantcompositions in a range of about 15% to about 20% by weight of thecementitious component.

In addition, the swellable particles that are utilized may have a widevariety of shapes and sizes of individual particles suitable for use inaccordance with embodiments of the present invention. By way of example,the swellable particles may have a well-defined physical shape as wellas an irregular geometry, including the physical shape of platelets,shavings, fibers, flakes, ribbons, rods, strips, spheroids, beads,pellets, tablets, or any other physical shape. In some embodiments, theswellable particles may have a particle size in the range of about 5microns to about 1,500 microns. In some embodiments, the swellableparticles may have a particle size in the range of about 20 microns toabout 500 microns. However, particle sizes outside these defined rangesalso may be suitable for particular applications.

Other additives suitable for use in subterranean cementing operationsalso may be added to embodiments of the sealant compositions, inaccordance with embodiments of the present invention. Examples of suchadditives include, but are not limited to, strength-retrogressionadditives, set accelerators, set retarders, weighting agents,lightweight additives, gas-generating additives, mechanical propertyenhancing additives, lost-circulation materials, filtration-controladditives, dispersants, a fluid loss control additive, defoaming agents,foaming agents, thixotropic additives, and combinations thereof.Specific examples of these, and other, additives include crystallinesilica, amorphous silica, fumed silica, salts, fibers, hydratable clays,calcined shale, vitrified shale, microspheres, fly ash, slag,diatomaceous earth, metakaolin, rice husk ash, natural pozzolan (e.g.,pumicite), zeolite, cement kiln dust, lime, elastomers, elastomericparticles, resins, latex, combinations thereof, and the like. Oneexample of a suitable elastomeric particle comprises a block copolymerof a styrene butadiene rubber as set forth in U.S. Pat. No. 6,832,651,the disclosure of which is incorporated herein by reference. A personhaving ordinary skill in the art, with the benefit of this disclosure,will readily be able to determine the type and amount of additive usefulfor a particular application and desired result.

Embodiments of the sealant compositions of the present invention mayhave a density suitable for a particular application. By way of example,the sealant compositions may have a density in the range of from about 4pounds per gallon (“ppg”) to about 20 ppg. In certain embodiments, thesealant compositions may have a density in the range of from about 8 ppgto about 17 ppg. Embodiments of the sealant compositions may be foamedor unfoamed or may comprise other means to reduce their densities, suchas hollow microspheres, low-density elastic beads, or otherdensity-reducing additives known in the art. Those of ordinary skill inthe art, with the benefit of this disclosure, will recognize theappropriate density for a particular application.

As will be appreciated by those of ordinary skill in the art, certainembodiments of the sealant compositions of the present invention may beused for forming a seal in a variety of subterranean applications. Incertain embodiments, a sealant composition may be introduced into asubterranean formation and allowed to form a seal therein. In certainembodiments, the sealant composition may comprise a cement compositionthat sets in the subterranean formation to form the seal. By way ofexample, in certain primary cementing embodiments, a sealant compositionmay be introduced into a space between a subterranean formation and apipe string located in the subterranean formation. The sealantcomposition may be allowed to set to form a hardened mass in the spacebetween the subterranean formation and the pipe string. Embodiments ofthe present invention further may comprise running the pipe string intoa well bore penetrating the subterranean formation. In addition, incertain remedial cementing embodiments, a sealant composition may beused, for example, in squeeze-cementing operations or in the placementof cement plugs. For example, embodiments of the sealant compositionsmay be used to: penetrate a gravel pack to shut off water or gasproduction, penetrate a gravel pack to divert steam injections, andpenetrate a gravel pack to plug and abandon a well. One or morehydrocarbons (e.g., oil, gas, etc.) may be produced from a well borepenetrating the subterranean formation in accordance with embodiments ofthe present invention.

In addition to incorporation of the nano-particles in a dry free-flowingstate, embodiments of the present invention may include incorporatingthe nano-particles in an agglomerated form. Among other things, use ofagglomerated nano-particles should facilitate the use of nano-particlesin subterranean applications, for example, by alleviating potentialhandling problems. In general, agglomerated nano-particles may includediscrete nano-particles that have been collected to form a cohesivemass. Any of a variety of different techniques may be used toagglomerate the nano-particles for use in embodiments of the presentinvention. In certain embodiments, agglomerated nano-particles maycomprise nano-particles bound together by a water-soluble binder. By wayof example, agglomerated nano-particles may be prepared by depositingthe water-soluble binder onto the nano-particles such that the binderholds the nano-particles together. Agglomerated nano-particles also mayinclude nano-particles that have been pelletized. Generally, thenano-particles may be formed into pellets of any desired shape and/orsize by any suitable technique, including, but not limited to,compression, extrusion, and casting. Example methods of agglomerationare set forth in U.S. Pat. Nos. 5,454,867; 6,500,253; 6,861,392; and7,156,174, the disclosures of which are incorporated herein byreference.

Agglomeration of the nano-particles generally may aid with mixing andbulk transfer of nano-particles. However, when the agglomeratednano-particles are contacted with water, the agglomerated nano-particleshould disperse into discrete nano-particles in accordance withembodiments of the present invention. For example, the agglomeratednano-particles may be designed to immediately disperse into discretenano-particles when mixed with water. By way of further example, theagglomerated nano-particles may be designed to disperse after a chosendelay period. In certain embodiments, a degradable material may beincorporated into the agglomerated nano-particles, for example, tofacilitate delayed release of the nano-particles. Examples of suitabledegradable materials include, but are not limited to, a dextran, acellulose, a chitin, a chitosan, a liquid ester (e.g., triethylcitrate), a protein (e.g., gelatin), an aliphatic polyester (e.g.,polylactic acid), a poly(glycolide), a poly(e-caprolactone), a poly(hydroxybutyrate), a poly(anhydride), an aliphatic polycarbonate, anortho ester, a poly(orthoester), a poly(amino acid), a poly (ethyleneoxide), a polyphosphazene, and combinations thereof.

Another technique for alleviated potential handling problems associatedwith incorporation of the nano-particles in a dry free-flowing state mayinclude incorporating nano-particles a liquid suspension (e.g., colloidsuspension). For example, the nano-particles dispersed in a continuousliquid phase may be incorporated into embodiments of the sealantcompositions. Suspension of the nano-particles in a liquid mediumgenerally may aid with mixing and bulk transfer of nano-particles, butthe nano-particles should release from the suspension when mixed withthe sealant composition in accordance with present embodiments.

Contained nano-particles also may be used in certain embodiments of thepresent invention. Specifically, containment of the nano-particles inaccordance with embodiments of the present invention may includeenclosing the nano-particles within an outer coating or container inparticulate form. Certain methods of encapsulation are set forth in U.S.Pat. Nos. 5,373,901; 6,444,316; 6,527,051; 6,554,071; 7,156,174; and7,204,312, the disclosures of which are incorporated herein byreference.

Various types of containment may be employed, in certain embodiments,such that the nano-particles (e.g., the nano-hydraulic cement) arecontained but retain their particulate nature and, thus, retain theircorresponding impact on physical properties of sealant composition. Forexample, the nano-particles may be contained within a bag, capsule,layer, coating or the like. Further, the material utilized to containthe nano-particles may be selected to facilitate transportation and/orincorporation of the nano-particles into a sealant composition. Forexample, to facilitate handling of the nano-particles and/or tofacilitate timed release of the nano-particles, the containment materialmay be degradable. This may facilitate handling of the nano-particles byallowing inclusion of the contained nano-particles in a sealantcomposition without requiring that the nano-particles first be removedfrom the containment material. Further, the containing material may bedesigned to degrade at a certain rate when in contact with certainmaterials (e.g., water) so that the nano-particles are released into thesealant composition at a desired time. Certain water-dissolvablematerials that may be utilized to encapsulate the nano-particles aredescribed in U.S. Pat. Nos. 4,961,790 and 5,783,541, the disclosures ofwhich are incorporated herein by reference.

In accordance with certain embodiments, the sealant compositions of thepresent invention may utilize a packing volume fraction suitable for aparticular application as desired. As used herein, the term “packingvolume fraction” refers to the volume of the particulate materials in afluid divided by the total volume of the fluid. The size ranges of thepreferred particulate materials are selected, as well as theirrespective proportions, in order to provide a maximized packing volumefraction so that the fluid is in a hindered settling state. It is knownthat, in such a state, the particulate materials behave “collectively”like a porous solid material. The hindered settling state is believed tocorrespond, in practice, to a much higher solid material concentrationin the fluid than that present in the some traditional sealantcompositions. Packing volume fraction is described in further detail inU.S. Pat. No. 7,213,646, the disclosure of which is incorporated hereinby reference.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein. Theparticular embodiments disclosed above are illustrative only, as thepresent invention may be modified and practiced in different butequivalent manners apparent to those skilled in the art having thebenefit of the teachings herein. Furthermore, no limitations areintended to the details of construction or design herein shown, otherthan as described in the claims below. It is therefore evident that theparticular illustrative embodiments disclosed above may be altered ormodified and all such variations are considered within the scope andspirit of the present invention. While compositions and methods aredescribed in terms of “comprising,” “containing,” “having,” or“including” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsand steps. Whenever a numerical range with a lower limit and an upperlimit is disclosed, any number and any included range falling within therange is specifically disclosed. In particular, every range of values(of the form, “from about a to about b,” or, equivalently, “fromapproximately a to b,” or, equivalently, “from approximately a-b”)disclosed herein is to be understood to set forth every number and rangeencompassed within the broader range of values. Also, the terms in theclaims have their plain, ordinary meaning unless otherwise explicitlyand clearly defined by the patentee.

What is claimed is:
 1. A sealant composition comprising: nano-particlescomprising nano-hydraulic cement and additional nano-particles selectedfrom the group consisting of nano-silica, nano-clay, nano-alumina,nano-zinc oxide, nano-boron, nano-iron oxide, and any combinationthereof, and water in an amount of about 33% to about 200% by weight ofcementitious materials present in the sealant composition, wherein thenano-particles comprise at least 75% by weight of dry particles in thesealant composition, and wherein no additional dry particles other thanthe dry particles were included in the sealant composition.
 2. Thesealant composition of claim 1 wherein the nano-particles comprise atleast about 90% by weight of the dry particles in the sealantcomposition.
 3. The sealant composition of claim 1 wherein the sealantcomposition further comprises at least one additive selected from thegroup consisting of a strength-retrogression additive, a setaccelerator, a set retarder, a weighting agent, a lightweight additive,a gas-generating additive, a mechanical property enhancing additive, alost-circulation material, a filtration-control additive, a dispersant,a fluid loss control additive, a defoaming agent, a foaming agent, athixotropic additive, and any combination thereof.
 4. The sealantcomposition of claim 1 wherein the sealant composition further comprisesat least one additive selected from the group consisting of crystallinesilica, amorphous silica, fumed silica, salt, fiber, hydratable clay,calcined shale, vitrified shale, a microsphere, fly ash, slag,diatomaceous earth, metakaolin, rice husk ash, natural pozzolan,pumicite, zeolite, cement kiln dust, lime, an elastomer, an elastomericparticle, resin, latex, a swellable particle, and any combinationthereof.
 5. The sealant composition of claim 1 wherein the sealantcomposition has a maximized packing volume fraction, wherein themaximized packing volume fraction uses particulate material includingthe nano-particles.
 6. The sealant composition of claim 1 wherein atleast a portion of the nano-particles are agglomerated nano-particles,wherein a degradable material is incorporated into the agglomeratednano-particles to facilitate delayed release of the portionnano-particles in the sealant composition.
 7. A sealant compositioncomprising: nano-particles comprising nano-hydraulic cement andadditional nano-particles selected from the group consisting ofnano-silica, nano-clay, nano-alumina, nano-zinc oxide, nano-boron,nano-iron oxide, and any combination thereof, and water in an amount ofabout 33% to about 200% by weight of cementitious materials present inthe sealant composition, wherein the nano-particles comprise at leastabout 75% by weight of dry particles in the sealant composition, andwherein at least a portion of the nano-particles are introduced into thesealant composition in a liquid suspension, and wherein no additionaldry particles other than the dry particles were included in the sealantcomposition.
 8. The sealant composition of claim 7 wherein thenano-particles comprise at least about 90% by weight of the dryparticles in the sealant composition.
 9. The sealant composition ofclaim 7 wherein the sealant composition further comprises at least oneadditive selected from the group consisting of a strength-retrogressionadditive, a set accelerator, a set retarder, a weighting agent, alightweight additive, a gas-generating additive, a mechanical propertyenhancing additive, a lost-circulation material, a filtration-controladditive, a dispersant, a fluid loss control additive, a defoamingagent, a foaming agent, a thixotropic additive, and any combinationthereof.
 10. The sealant composition of claim 7 wherein the sealantcomposition further comprises at least one additive selected from thegroup consisting of crystalline silica, amorphous silica, fumed silica,salt, fiber, hydratable clay, calcined shale, vitrified shale, amicrosphere, fly ash, slag, diatomaceous earth, metakaolin, rice huskash, natural pozzolan, pumicite, zeolite, cement kiln dust, lime, anelastomer, an elastomeric particle, resin, latex, a swellable particle,and any combination thereof.
 11. A sealant composition comprising:agglomerated nano-particles wherein the agglomerated nano-particlescomprise at least one degradable material selected from the groupconsisting of a dextran, a cellulose, a chitin, a chitosan, a liquidester, a protein, an aliphatic polyester, a poly(glycolide), apoly(e-caprolactone), a poly (hydroxybutyrate), a poly(anhydride), analiphatic polycarbonate, an ortho ester, a poly(orthoester), apoly(amino acid), a poly (ethylene oxide), a polyphosphazene, and anycombination thereof, and water.
 12. The sealant composition of claim 11wherein the agglomerated nano-particles comprise at least about 20% byweight of the dry particles in the sealant composition.
 13. The sealantcomposition of claim 11 wherein the agglomerated nano-particles compriseat least about 50% by weight of the dry particles in the sealantcomposition.
 14. The sealant composition of claim 11 wherein theagglomerated nano-particles comprise at least one nano-particle selectedfrom the group consisting of a nano-hydraulic cement, a nano-silica, anano-clay, a nano-alumina, a nano-zinc oxide, a nano-boron, a nano-ironoxide, and any combination thereof.
 15. The sealant composition of claim11 wherein the agglomerated nano-particles comprise nano-particles boundtogether by a water-soluble binder.
 16. The sealant composition of claim11 wherein the agglomerated nano-particles comprise pelletizednano-particles.
 17. The sealant composition of claim 11 wherein thesealant composition further comprises at least one additive selectedfrom the group consisting of a strength-retrogression additive, a setaccelerator, a set retarder, a weighting agent, a lightweight additive,a gas-generating additive, a mechanical property enhancing additive, alost-circulation material, a filtration-control additive, a dispersant,a fluid loss control additive, a defoaming agent, a foaming agent, athixotropic additive, and any combination thereof.
 18. The sealantcomposition of claim 11 wherein the sealant composition furthercomprises at least one additive selected from the group consisting ofcrystalline silica, amorphous silica, fumed silica, salt, fiber,hydratable clay, calcined shale, vitrified shale, a microsphere, flyash, slag, diatomaceous earth, metakaolin, rice husk ash, naturalpozzolan, pumicite, zeolite, cement kiln dust, lime, an elastomer, anelastomeric particle, resin, latex, a swellable particle, and anycombination thereof.
 19. The sealant composition of claim 11 wherein thenano-particles further comprise nano-hydraulic cement and additionalnano-particles selected from the group consisting of nano-silica,nano-clay, nano-alumina, nano-zinc oxide, nano-boron, nano-iron oxide,and any combination thereof, wherein the water is present in an amountof about 33% to about 200% by weight of cementitious materials presentin the sealant composition.
 20. The sealant composition of claim 19wherein the nano-particles comprise at least about 75% by weight of dryparticles in the sealant composition, wherein at least a portion of thenano-particles are introduced into the sealant composition in a liquidsuspension, and wherein no additional dry particles other than the dryparticles were included in the sealant composition.
 21. A sealantcomposition comprising: nano-particles comprising nano-hydraulic cementand additional nano-particles selected from the group consisting ofnano-silica, nano-clay, nano-alumina, nano-zinc oxide, nano-boron,nano-iron oxide, and any combination thereof, a at least one particleselected from the group consisting of an elastomeric particle and aswellable particle, and water in an amount of about 33% to about 200% byweight of cementitious materials present in the sealant composition,wherein the nano-particles comprise at least about 75% by weight of dryparticles in the sealant composition, wherein at least a portion of thenano-particles are introduced into the sealant composition in a liquidsuspension, and wherein no additional dry particles other than the dryparticles were included in the sealant composition.
 22. The sealantcomposition of claim 21 wherein the nano-particles comprise at least onenano-particle selected from the group consisting of a nano-hydrauliccement, a nano-silica, a nano-clay, a nano-alumina, a nano-zinc oxide, anano-boron, a nano-iron oxide, and any combination thereof.
 23. Thesealant composition of claim 21 wherein the elastomeric particlecomprises a block copolymer of styrene butadiene rubber.
 24. The sealantcomposition of claim 21 wherein the swellable particle is waterswellable or oil swellable.